WO2019168718A1 - Polyoléfine rotomoulée ignifuge - Google Patents

Polyoléfine rotomoulée ignifuge Download PDF

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Publication number
WO2019168718A1
WO2019168718A1 PCT/US2019/018711 US2019018711W WO2019168718A1 WO 2019168718 A1 WO2019168718 A1 WO 2019168718A1 US 2019018711 W US2019018711 W US 2019018711W WO 2019168718 A1 WO2019168718 A1 WO 2019168718A1
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Prior art keywords
article
plastic article
article according
bis
melamine cyanurate
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PCT/US2019/018711
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English (en)
Inventor
John A. SIGLER
Thomas F. THOMPSON
Stephen M. ANDREWS
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Basf Se
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Priority to CN201980015477.8A priority Critical patent/CN112166148A/zh
Priority to US16/967,612 priority patent/US12012542B2/en
Priority to EP19760143.8A priority patent/EP3759165A4/fr
Priority to MX2020008934A priority patent/MX2020008934A/es
Priority to BR112020017274-0A priority patent/BR112020017274A2/pt
Priority to CA3089890A priority patent/CA3089890A1/fr
Priority to JP2020544904A priority patent/JP2021515074A/ja
Publication of WO2019168718A1 publication Critical patent/WO2019168718A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/04—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould
    • B29C41/06—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould about two or more axes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34928—Salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C08K5/5357—Esters of phosphonic acids cyclic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/04—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould
    • B29C41/042—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould by rotating a mould around its axis of symmetry
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/0633—LDPE, i.e. low density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0026—Flame proofing or flame retarding agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2022/00—Hollow articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives

Definitions

  • Flame Retardant Rotomolded Polyolefin The disclosure is directed to flame retardant polyolefin compositions prepared by a rotomolding process.
  • Background Rotational molding is a manufacturing process in which hollow plastic articles are prepared. In general, a plastic material is filled into one half of a mold which is then closed with the other half. The closed mold is heated and rotated around different axes, wherein molten polymer coats the interior of the mold– a process referred to as “sintering”. The mold is then cooled and the molded article removed. The process may require temperatures of greater than about 300°C or even greater than about 400°C.
  • the rotomolding process may be employed to prepare articles such as storage tanks for water, oil and the like; kayaks, toys, refuse containers, equipment housings, etc.
  • a rotomolding process employs a polyolefin substrate, for instance polyethylene.
  • Flame retardancy is a particular concern for many of the articles produced by the rotomolding process.
  • Conventional flame retardants are generally employed at high loadings, which may result in a severe reduction in desired mechanical properties of rotomolded parts, such as impact strength and ductility.
  • rotomolded articles are relatively thick, which also contributes to difficulty in finding effective flame retardants.
  • high levels of flame retardants may interfere with the plastic sintering process.
  • a flame-retardant hollow plastic article comprising a polyolefin substrate, the polyolefin substrate having incorporated therein a phosphonate ester, an N-alkoxy hindered amine and melamine cyanurate. Also disclosed is a flame retardant additive mixture comprising a phosphonate ester, an N-alkoxy hindered amine and melamine cyanurate, wherein a weight/weight ratio of phosphonate ester to melamine cyanurate is from about 7/1 to about 1/1 and a
  • a weight/weight ratio of melamine cyanurate to N-alkoxy hindered amine is from about 8/1 to about 1/1.
  • a process for the production of a hollow plastic article comprising incorporating into a polyolefin substrate a phosphonate ester, an N-alkoxy hindered amine and melamine cyanurate to provide a fully formulated polyolefin mixture, adding the mixture to a mold, heating the mold to a temperature of greater than 280°C, rotating the mold about at least 2 axes, wherein molten polyolefin mixture coats the interior of the mold, cooling the mold while still rotating, opening the mold and removing the formed hollow article.
  • a polyolefin substrate comprises a polyethylene.
  • Polyethylene includes, for example, high density polyethylene (HDPE), high molecular weight high density polyethylene (HMW HDPE), ultrahigh molecular weight high density polyethylene (UHMW HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE) or polyethylenes and ethylene copolymers prepared using Phillips catalysts and polyethylene blends.
  • HDPE high density polyethylene
  • HMW HDPE high molecular weight high density polyethylene
  • UHMW HDPE ultrahigh molecular weight high density polyethylene
  • MDPE medium density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • BLDPE branched low density polyethylene
  • Ethylene copolymers may contain differing proportions of comonomers.
  • comonomers include 1-olefins such as propene, 1- butene, 1-pentene, 1-hexene, 1-heptene, 1-octene or isobutylene, styrene, cycloolefins such as cyclopentene, cyclohexene or norbornene or dienes such as butadiene, isoprene, 1,4- hexadiene, cyclopentadiene, dicyclopentadiene, norbornadiene or ethylidenenorbornene.
  • Polyolefin substrates also include polyethylene blends with polyolefins.
  • Examples include mixtures of polyethylene with polypropylene (PP) and mixtures of various PE types, for example mixtures including two or more of high density polyethylene (HDPE), high molecular weight high density polyethylene (HMW HDPE), ultrahigh molecular weight high density polyethylene (UHMW HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE) or ethylene-propylene-diene terpolymers (EPDM) containing high proportions of diene.
  • HDPE high density polyethylene
  • HMW HDPE high molecular weight high density polyethylene
  • UHMW HDPE ultrahigh molecular weight high density polyethylene
  • MDPE medium density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • BLDPE branched low density polyethylene
  • EPDM ethylene-propylene-diene terpolymers
  • polymers can be linear or branched and can be formulated with or without crosslinking (e.g., chemical crosslinking).
  • the polyolefin substrate may have other polymers incorporated therein, for example polystyrene, polyamide, polyester, polycarbonate, epoxy resins, polyurethane, copolymers thereof (e.g., random or block copolymers) or mixtures thereof.
  • such “other” polymers may be present in a finished article from any of about 1 wt% (weight percent), about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt% or about 7 wt% to any of about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt% or about 15 wt%, based on the total weight of the finished article.
  • the phosphonate ester is of formula
  • R 1 and R 2 are independently alkyl, substituted alkyl, aralkyl, substituted aralkyl, aryl or substituted aryl.
  • R 1 and R 2 are independently benzyl or C 1 -C 10 straight or branched chain alkyl.
  • R 1 and R 2 are independently benzyl or C 1 -C 4 straight or branched chain alkyl.
  • R 1 and R 2 are independently benzyl or methyl.
  • a phosphonate ester wherein R 1 and R 2 are methyl is commercially available as AFLAMMIT PCO 960.
  • N-alkoxy hindered amines include one or more moieties of formula
  • R 1 , R 2 , R 3 and R 4 are each independently C 1 -C 8 alkyl or R 1 and R 2 together and/or R 3 and R 4 together with the linking carbon form cyclohexyl and R 5 is a hydrocarbyl group.
  • R 5 is propyl, octyl, 2-hydroxy-2-methylpropyl, decyl, undecyl, dodecyl, cyclohexyl or a hydrocarbyl containing from 50 to 1000 carbon atoms.
  • each of R1, R2, R3 and R4 are methyl.
  • an N-alkoxy hindered amine is selected from a group consisting of formula (1) through (9):
  • n is an integer from 1 to 15 or is an integer from 1 to 10 or from 1 to 5;
  • R6 is a group of formula
  • R 7 is C 1 -C 18 alkyl or C 1 -C 18 hydroxyalkyl
  • R 8 and R 8 ’ are independently C 1 -C 30 alkyl
  • R 9 and R 9 ’ are independently C 1 -C 30 alkyl or cylclohexyl;
  • n is an integer of from any of 1, 2, 3 or 4 to any of 5, 6, 7, 8, 9 or 10, R 10 is C 1 -C 40 alkyl and
  • W is a hydrocarbyl containing from 50 to 1000 carbon atoms
  • n is an integer from any of 1, 2, 3, 4, 5, 6, 7 or 8 to any of 9, 10, 11, 12, 15, 18, 21, 24, 27, 30, 33, 36, 39, 42, 45, 47 or 50 and
  • W is a hydrocarbyl containing from 50 to 1000 carbon atoms.
  • R 7 is C 1 -C 4 alkyl or C 1 - C 4 hydroxyalkyl.
  • R 7 is 2-hydroxy-2-methylpropyl.
  • a compound of formula (5) in certain embodiments is 1-(2-hydroxy-2-methylpropoxy)-4- octadecanoyloxy-2,2,6,6-tetramethylpiperidine.
  • R 8 and R 8 ’ are independently C 1 -C 20 alkyl or C 8 -C 20 alkyl.
  • R 8 and R 8 ’ are independently decyl, undecyl, or dodecyl.
  • R 9 and R 9 ’ are independently C 1 -C 10 alkyl or cyclohexyl.
  • R 9 and R 9 ’ are octyl.
  • R 5 is C 11 -C 20 alkyl.
  • W is a hydrocarbyl of from 50 carbon atoms to 500 carbon atoms or to 800 carbon atoms.
  • N-alkoxy hindered amines contain one or more moieties of formula .
  • N-alkoxy hindered amines contain one or more moieties of formula
  • N-alkoxy hindered amines contain one or more moieties of formula
  • Alkyl groups may be linear or branched and may include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1- methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3- tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, tert-octyl, 2-ethylhexyl, 1,1,3- trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl and dodecyl.
  • Aralkyl may be a C 7 -C 12 aralkyl, for example benzyl or cumyl.
  • Aryl includes for instance phenyl and naphthyl.
  • alkyl, aryl or aralkyl may in some embodiments be substituted by one or more C1-C4 alkyl, hydroxyl, carboxylic, amino or thiol groups.
  • Hydrocarbyl is any hydrocarbon containing group, for example straight or branched chain alkyl or alkenyl which may be interrupted by or substituted by one or more heteroatom- containing groups or aryl groups, for instance interrupted by one or more–O-,–NH- or– C(O)O- groups and/or substituted by one or more hydroxyl, carboxylic, amino, thiol, phosphonate or aryl groups.
  • Melamine cyanurate is a salt formed from melamine and cyanuric acid, and may be obtained, for example, by the reaction of about equimolar quantities of melamine and cyanuric acid. Melamine cyanurate is commercially available, for example, as MELAPUR MC (BASF).
  • Melamine cyanurate may have an average particle size of less than about 50 microns, in some embodiments less than about 35 microns; and in certain embodiments about 25 microns or less.
  • melamine cyanurate in some embodiments may have a D50 particle size of from any of about 1 ⁇ m, about 2 ⁇ m, about 3 ⁇ m, about 4 ⁇ m, about 5 ⁇ m, about 6 ⁇ m, about 7 ⁇ m, about 8 ⁇ m or about 9 ⁇ m to any of about 10 ⁇ m, about 12 ⁇ m, about 15 ⁇ m, about 18 ⁇ m, about 21 ⁇ m, about 24 ⁇ m, about 27 ⁇ m, about 30 ⁇ m, about 33 ⁇ m, about 36 ⁇ m, about 39 ⁇ m or about 42 ⁇ m.
  • particle size is synonymous with particle diameter and is determined for instance by scanning electron microscopy (SEM) or transmission electron microscopy (TEM). Average particle size is synonymous with D50, meaning half of the population resides above this point, and half below.
  • Particle size refers to primary particles. Particle size may be measured by laser light scattering techniques, with dispersions or dry powders.
  • Present hollow articles may in some embodiments comprise a phosphonate ester from any of about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt% or about 10 wt% to any of about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%, about 15 wt%, about 16 wt%, about 17 wt%, about 18 wt%, about 19 wt% or about 20 wt%, based on the total weight of the article.
  • the hollow articles may comprise an N-alkoxy hindered amine from any of about 0.1 wt%, about 0.3 wt%, about 0.6 wt%, about 0.9 wt%, about 1.0 wt%, about 1.3 wt% or about 1.6 wt% to any of about 1.8 wt%, about 2.0 wt%, about 2.3 wt%, about 2.6 wt%, about 2.9 wt%, about 3.2 wt%, about 3.5 wt%, about 3.8 wt%, about 4.1 wt%, about 4.4 wt%, about 4.7 or about 5.0 wt%, based on the total weight of the article.
  • the hollow articles may comprise melamine cyanurate from any of about 1.0 wt%, about 1.3 wt%, about 1.6 wt%, about 1.9 wt%, about 2.0 wt%, about 2.3 wt% or about 2.6 wt%, about 2.8 wt%, about 3.0 wt%, about 3.3 wt%, about 3.6 wt%, about 3.9 wt%, about 4.2 wt%, about 4.5 wt%, about 4.8 wt% or about 5.1 wt% to any of about 5.4 wt%, about 5.7, about 6.0 wt%, about 6.3 wt%, about 6.6 wt%, about 6.9 wt%, about 7.2 wt%, about 7.5 wt%, about 7.8 wt%, about 8.1 wt%, about 8.4 wt%, about 8.7 wt%, about 9.0 wt%, about 9.3 wt
  • a weight/weight ratio of phosphonate ester to melamine cyanurate is from any of about 7/1, about 6/1, about 5/1 or about 4/1 to any of about 3/1, about 2/1 or about 1/1.
  • a weight/weight ratio of melamine cyanurate to N-alkoxy (NOR) hindered amine is from any of about 8/1, about 7/1, about 6/1 or about 5/1 to any of about 4/1, about 3/1, about 2/1 or about 1/1.
  • the hollow articles comprise the polyolefin substrate from any of about 50 wt%, about 55 wt%, about 60 wt%, about 65 wt%, about 70 wt%, about 73 wt%, about 76 wt%, about 79 wt% or about 82 wt% to any of about 85 wt%, about 88 wt%, about 90 wt%, about 93 wt% or about 95 wt%, based on the total weight of the article.
  • one or more further additives may be incorporated into the hollow articles of the invention.
  • UVAs ultraviolet light absorbers
  • UVAs further hindered amine stabilizers
  • antioxidants include one or more additives selected from a group consisting of ultraviolet light absorbers (UVAs), further hindered amine stabilizers and antioxidants.
  • UV light absorbers may be selected from a group consisting of hydroxyphenylbenzotriazole, tris-aryl-s-triazine, hydroxybenzoate, 2-hydroxybenzophenone and cyanoacrylate ultraviolet light absorbers (UVAs). Hydroxyphenylbenzotriazole UVAs are for instance disclosed in U.S. Pat. Nos.
  • UV absorbers are for instance esters of substituted and unsubstituted benzoic acids, as for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert- butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert- butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • 2-Hydroxybenzophenone UV absorbers are for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'- dimethoxy derivatives.
  • Cyanoacrylate UV absorbers are for instance pentaerythritol tetrakis(2-cyano-3,3- diphenylacrylate), ⁇ -cyano- ⁇ , ⁇ -diphenylacrylic acid ethyl ester or isooctyl ester and ⁇ -cyano- ⁇ -methyl-p-methoxy-cinnamic acid methyl ester or butyl ester.
  • UVAs are commercial, for example TINUVIN 326, TINUVIN 234, TINUVIN 1577, TINUVIN 1600, CYASORB UV 1164, CYASORB THT, CYASORB UV 2908, CHIMASSORB 81, UVINUL 3030, etc.
  • Ultraviolet light absorbers may be present, in total, from any of about 0.20 wt%, about 0.25 wt%, about 0.30 wt%, about 0.35 wt%, about 0.40 wt%, about 0.45 wt%, about 0.50 wt%, about 0.55 wt%, about 0.60 wt%, about 0.65 wt%, about 0.70 wt% or about 0.75 wt% to any of about 0.80 wt%, about 0.85 wt%, about 0.90 wt%, about 0.95 wt%, about 1.0 wt%, about 1.2 wt%, about 1.5 wt%, about 1.7 wt% or about 2.0 wt%, based on the total weight of the hollow article.
  • Hindered amine light stabilizers are disclosed for example in US2015/0284535 and U.S. Pat. Nos.5,004,770, 5,204,473, 5,096,950, 5,300,544, 5,112,890, 5,124,378, 5,145,893, 5,216,156, 5,844,026, 5,980,783, 6,046,304, 6,117,995, 6,271,377, 6,297,299, 6,392,041, 6,376,584 and 6,472,456.
  • Hindered amine light stabilizers include for example: (1) 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine,
  • hindered amine light stabilizers may be selected from a group consisting of (2) bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,
  • Certain binary or ternary combinations of hindered amine light stabilizers may be advantageous. For instance, binary or ternary combinations: (2) bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate and
  • HALS (38) or (39) may be substituted for HALS (36) in the binary and ternary combinations.
  • Many of the present hindered amine stabilizers are commercial, for example
  • the weight/weight ratio is from any of about 1/19, about 1/18, about 1/17, about 1/16, about 1/15, about 1/14, about 1/13, about 1/12, about 1/11, about 1/10, about 1/9, about 1/8, about 1/7, about 1/6, about 1/5, about 1/4, about 1/3, about 1/2 or about 1/1 to any of about 1/2, about 1/3, about 1/4, about 1/5, about 1/6, about 1/7, about 1/8, about 1/9, about 1/10, about 1/11, about 1/12, about 1/13, about 1/14, about 1/15, about 1/16, about 1/17, about 1/18, about 1/19 or about 1/20.
  • a weight/weight ratios of any two of the HALS is as for the binary combinations.
  • a combination of a low molecular weight and a high molecular weight HALS may be employed.
  • the low molecular weight stabilizers have a molecular weight of from about 200 g/mol to about 1000 g/mol.
  • the high molecular weight stabilizers have a molecular weight from about 1200 g/mol to about 10,000 g/mol.
  • Some low molecular weight hindered amines are (1)-(33a).
  • Some high molecular weight hindered amines are (34)-(49).
  • the repeating unit“n” is a value such that the average molecular weight is from about 1200 g/mol to about 10,000 g/mol.
  • a low and high molecular weight hindered amine combination is employed together with a UV absorber, for instance an hydroxybenzoate UV absorber.
  • Further hindered amine light stabilizers may be present from any of about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.4 wt%, about 0.5 wt%, about 0.6 wt%, about 0.7 wt%, about 0.8 wt%, about 0.9 wt% to any of about 1.0 wt%, about 1.1 wt%, about 1.2 wt%, about 1.3 wt%, about 1.4 wt%, about 1.5 wt%, about 1.6 wt%, about 1.7 wt%, about 1.8 wt%, about 1.9 wt% or about 2.0 wt%, based on the total weight of the finished article.
  • Antioxidants may be selected from a group consisting of hindered phenolic antioxidants, organophosphorus stabilizers, dialkylhydroxylamine stabilizers, amine oxide stabilizers and tocopherols.
  • antioxidants include a combination of an organophosphorus stabilizer and a hindered phenolic antioxidant, a dialkylhydroxylamine stabilizer, a combination of an organophosphorus stabilizer and a dialkylhydroxylamine stabilizer, an amine oxide stabilizer or a combination of an organophosphorus stabilizer and an amine oxide stabilizer.
  • Antioxidants also include vitamin E and vitamin E acetate (tocopherols).
  • Organophosphorus stabilizers are for example known phosphite and phosphonite stabilizers and include triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di- ⁇ -cumylphenyl) pentaerythrtitol diphosphite, diisodecyl pent
  • Suitable organophosphorus stabilizers are also liquid stabilizers as disclosed in U.S. Pub. No.2010/048782 and U.S. Pat. No.7,888,414, for example liquid phosphites P-2, P-3 and P-4 therein.
  • Suitable liquid organophosphorus stabilizers are also disclosed in U.S. Pub. Nos.2013/0225736 and 2010/0029844 and U.S. Pat. Nos.7,468,410 and 8,304,477.
  • Hindered phenolic antioxidants include for example tris(3,5-di-tert-butyl-4- hydroxybenzyl) isocyanurate, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6- trimethylbenzene, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4- hydroxybenzylphosphonic acid, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] or octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate.
  • a combination of an organophosphorus stabilizer and a hindered phenolic antioxidant may be tris(2,4-di-tert-butylphenyl) phosphite and pentaerythritol tetrakis [3-(3,5-di-tert-butyl- 4-hydroxyphenyl) propionate] or octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate.
  • a weight/weight ratio of organophosphorus stabilizer to hindered phenolic antioxidant may be from any of about 9/1, about 8/1, about 7/1, about 6/1, about 5/1, about 4/1, about 3/1, about 2/1 or about 1/1 to any of about 1/2, about 1/3, about 1/4, about 1/5, about 1/6, about 1/7, about 1/8 or about 1/9.
  • Hydroxylamine stabilizers are for example N,N-dibenzylhydroxylamine, N,N- diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N- didodecylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-tetradecylhydroxylamine, N-hexadecyl-N- heptadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N- octadecylhydroxylamine, N-methyl-N-octadecylhydroxylamine or N,N-di(C 16 - C 18 alkyl)
  • the amine oxide stabilizer is for instance a di(C 16 -C 18 )alkyl methyl amine oxide, CAS# 204933-93-7.
  • a combination of an organophosphorus stabilizer and a dialkylhydroxylamine is for example tris(2,4-di-tert-butylphenyl) phosphite and N,N-di(C 16 -C 18 alkyl)hydroxylamine.
  • a combination of an organophosphorus stabilizer and an amine oxide stabilizer is for example tris(2,4-di-tert-butylphenyl) phosphite and di(C 16 -C 18 )alkyl methyl amine oxide.
  • a weight/weight ratio of these combinations may be from any of about 9/1, about 8/1, about 7/1, about 6/1, about 5/1, about 4/1, about 3/1, about 2/1 or about 1/1 to any of about 1/2, about 1/3, about 1/4, about 1/5, about 1/6, about 1/7, about 1/8 or about 1/9.
  • Antioxidants may be present, in total, from any of about 0.10 wt%, about 0.20 wt%, about 0.30 wt%, about 0.40 wt%, about 0.50 wt% or about 0.60 wt% to any of about 0.70 wt%, about 0.80 wt%, about 0.90 wt% or about 1.0 wt%, based on the total weight of the hollow article.
  • Pigments include inorganic pigments, such as titanium dioxide in its three crystalline forms: rutile, anatase, or brookite, ultramarine blue, iron oxides, bismuth vanadates, carbon black, effect pigments including metallic pigments such as aluminum flake and pearlescent pigments such as micas, and organic pigments, for example phthalocyanines, perylenes, azo compounds, isoindolines, quinophthalones, diketopyrrolopyrroles, quinacridones, dioxazines, and indanthrones.
  • inorganic pigments such as titanium dioxide in its three crystalline forms: rutile, anatase, or brookite, ultramarine blue, iron oxides, bismuth vanadates, carbon black, effect pigments including metallic pigments such as aluminum flake and pearlescent pigments such as micas
  • organic pigments for example phthalocyanines, perylenes, azo compounds, isoindolines, quinophthalones,
  • Pigments may be included singly or in any combination in amounts typically of up to about 5% by weight, based on the total weight of the article.
  • Dyes are any of the colorants which dissolve completely in the plastic used or are present in molecularly dispersed form and therefore can be used to provide high-transparency, non- diffusion coloring of polymers.
  • Other dyes are organic compounds which fluoresce in the visible portion of the electromagnetic spectrum, e.g. fluorescent dyes.
  • Dyes may be included singly or in any combination in amounts typically of up to about 5% by weight, based on the total weight of the article.
  • Particulate fillers may be present in an amount from any of about 0.01 wt%, about 0.1 wt%, about 1 wt%, about 5 wt%, about 10 wt%, about 15 wt% or about 20 wt% to any of about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt% or about 50 wt%, based on the total weight of the article.
  • Fillers include but are not limited to titanium dioxide, silicon carbide, silica (and other oxides of silica, precipitated or not), antimony oxide, lead carbonate, zinc white, lithopone, zircon, corundum, spinel, apatite, barytes powder, barium sulfate, carbon black, dolomite, calcium carbonate, talc and hydrotalcite compounds of the ions Mg, Ca, or Zn with Al, Cr or Fe and CO 3 and/or HPO 4 , hydrated or not; quartz powder, hydrochloric magnesium carbonate, glass fibers, clays, alumina, and other metal oxides and carbonates, metal hydroxides, chrome, phosphorous, antimony trioxide, silica, silicone, and blends thereof.
  • fillers may include any other fillers and porous fillers and supports known in the art.
  • Still further additives may be incorporated into the polyolefin substrate, for instance additives such as anti-static agents (antistats), antiscratch additives, slip agents, polymer processing aids, etc. (see Plastic Additives Handbook; 6 th Edition). Included are metal salts of fatty acids, for example, calcium, magnesium, zinc, or aluminum stearate.
  • Further additives also include thiosynergists, for example dilauryl thiodipropionate or distearyl thiodipropionate.
  • Further additives also include benzofuranone stabilizers, for example those disclosed in U.S. Pat.
  • Further additives also include compatibilizers or dispersing aids, for example, maleic anhydride grafted PE or PP, poly(ethylene-co-vinyl acetate), poly(ethylene-acrylic acid), etc.
  • the further additives may be present from any of about 0.1 wt%, 0.2 wt%, about 0.5 wt%, about 0.7 wt% or about 1.0 wt% to any of about 1.5 wt%, about 2.0 wt%, about 2.5 wt%, about 3.0 wt%, about 3.5 wt%, about 4.0 wt%, about 4.5 wt% or about 5.0 wt%, based on a total weight of the article.
  • Rotomolding is used for the production of fairly large plastic hollow articles which may be reinforced with glass fibers.
  • the process includes filling one half of a mold with the plastic material.
  • the mold is then closed with the other half and heated and rotated in an oven such that the molten plastic spreads to the walls of the mold while being rotated around different axes.
  • the hollow article is obtained after cooling. In this manner it is possible to produce, for example, storage tanks from HD polyethylene.
  • the process requires heating a polyolefin mixture to temperatures in the range of from any of about 170°C, about 190° , about 210°C, about 230°C, about 240°C, about 260°C or about 280°C to any of about 300°C, about 340°C to about 370°C or about 400°C or higher. These temperatures represent the peak internal air temperature (PIAT) of an oven.
  • PIAT peak internal air temperature
  • Incorporation of the phosphonate ester, N-alkoxy hindered amine, melamine cyanurate (present additives) and optional further additives into the polyolefin substrate is carried out by known methods, for example before or after molding or also by applying the dissolved or dispersed additive mixture to the polyolefin, with or without subsequent evaporation of the solvent.
  • Present additives can also be added to the polyolefin in the form of a masterbatch which contains the additives in a concentration of, for example, about 2.5% to about 40% by weight, based on the total weight of the masterbatch.
  • the polymer of the masterbatch need not be the same as the polyolefin substrate.
  • Molding is carried out with known mixing machines, for instance mixers, kneaders or extruders.
  • Present additives and optional further additives can be premixed or added individually.
  • Present additives and optional further additives can also be added before or during the polymerization or before crosslinking.
  • Present additives and optional further additives can be incorporated into the polymer to be made flame retardant in pure form or encapsulated in waxes, oils or polymers.
  • Present additives and optional further additives can also be sprayed onto the polyolefin substrate. They are able to dilute other additives or their melts so that they can be sprayed also together with these additives onto the polyolefin.
  • Addition by spraying during the deactivation of the polymerization catalysts may be advantageous, it being possible to carry out spraying using, for example, the steam used for deactivation.
  • a present process includes the measurement of raw materials by weight followed by dry blending of the ingredients.
  • the present additives and optional further additives are incorporated into the thermoplastic polyolefin substrate by melt blending in an extruder. The present additives and optional additives may be added together or separately.
  • the term“incorporating into a polyolefin” means melt blending, that is, subjecting a mixture to melt conditions at an elevated temperature.
  • a mixture may be fed to a melt mixing device such as an extruder at a constant feed rate to extrude the material into a desired form, for example pellets.
  • the pellets are a“fully formulated polyolefin substrate”.
  • the pellets may be ground to a small, generally uniform particle size, for example to an average particle size of from about 150 microns to about 500 microns prior to rotomolding.
  • the fully formulated polyolefin particles are filled into one half of a mold which is then closed with the other half. Molds are typically made of aluminum or steel. The closed mold is heated and rotated around different axes, wherein molten polymer coats the interior of the mold– a process referred to as“sintering”.
  • present rotomolded articles have an average wall thickness of ⁇ about 1.50 mm, ⁇ about 1.75 mm, ⁇ about 2.00 mm, ⁇ about 2.25 mm, ⁇ about 2.50 mm, ⁇ about 2.75 mm, ⁇ about 3.00 mm, ⁇ about 3.25 mm, ⁇ about 3.50 mm, ⁇ about 3.75 mm, ⁇ about 4.00 mm, ⁇ about 4.25 mm, ⁇ about 4.50 mm or ⁇ about 4.75 mm.
  • rotomolded articles have an average wall thickness of from any of about 1.50 mm, about 1.75 mm, about 2.00 mm, about 2.25 mm, about 2.50 mm, about 2.75 mm or about 3.00 mm to any of about 3.25 mm, about 3.50 mm, about 3.75 mm, about 4.00 mm, about 4.25 mm, about 4.50 mm, about 4.75 mm, about 5.00 mm, about 5.25 mm, about 5.50 mm, about 5.75 mm or about 6.00 mm.
  • present rotomolded articles achieve a V-0 rating according to the UL-94 V test.
  • UL-94 V test Ratings for the UL-94 V test are listed below; UL-94 Test for Flammability of Plastic Materials for Parts in Devices and Appliances, 5th Edition, October 29, 1996.
  • present rotomolded articles having an average wall thickness of 125 mil (3.175 mm) achieve a V-0 rating.
  • the articles“a” and“an” herein refer to one or to more than one (e.g. at least one) of the grammatical object. Any ranges cited herein are inclusive.
  • the term“about” used throughout is used to describe and account for small fluctuations.
  • “about” may mean the numeric value may be modified by ⁇ 5%, ⁇ 4%, ⁇ 3%, ⁇ 2%, ⁇ 1%, ⁇ 0.5%, ⁇ 0.4%, ⁇ 0.3%, ⁇ 0.2%, ⁇ 0.1% or ⁇ 0.05%. All numeric values are modified by the term“about” whether or not explicitly indicated. Numeric values modified by the term“about” include the specific identified value. For example“about 5.0” includes 5.0.
  • U.S. patents, U.S. patent applications and published U.S. patent applications discussed herein are hereby incorporated by reference. Unless otherwise indicated, all parts and percentages are by weight. Weight percent (wt%), if not otherwise indicated, is based on an entire composition free of any volatiles.
  • Additives are dry blended with low density polyethylene (LDPE, 0.935 g/cm 3 ) to provide the formulations in the table below. Additive levels are reported in parts by weight, based on 100 parts polyethylene. The dry blends are melt extruded into pellets.
  • LDPE low density polyethylene
  • CM Compression molding
  • IM Injection molding
  • RM rotomolding
  • pellets are ground to 35 mesh and placed in a laboratory scale FST M20“clamshell” aluminum mold, which is rotated biaxially in a gas-fired oven. Hot air is circulated by blowers in the chamber while the temperature is increased to 288°C over 16 minutes to provide a peak internal air temperature of 204°C. The temperature is maintained for 20 minutes. The oven is opened and is cooled over 24 minutes while still rotating. The mold is opened and the hollow article is removed. Results of flame retardancy according to UL-94 are also found in the table below. Each test is performed in quadruplicate. All samples are 125 mil thick (3.175 mm).
  • Ph ester is a phosphonate ester wherein R1 and R2 are methyl.
  • MC is melamine cyanurate with an average particle size of less than 15 microns.
  • NOR is 1-(2-hydroxy-2- methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine.
  • the LDPE contains a base stabilization of 500 ppm of pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (phenolic antioxidant), 1200 ppm tris(2,4-di-tert-butylphenyl) phosphite
  • ppm parts per million

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Moulding By Coating Moulds (AREA)

Abstract

La présente invention concerne des articles creux de polyoléfine rendue ignifuge préparés par l'intermédiaire d'un procédé de rotomoulage en incorporant à l'intérieur un ester phosphonate, une amine bloquée N-alcoxy et du cyanurate de mélamine.
PCT/US2019/018711 2018-02-27 2019-02-20 Polyoléfine rotomoulée ignifuge WO2019168718A1 (fr)

Priority Applications (7)

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CN201980015477.8A CN112166148A (zh) 2018-02-27 2019-02-20 阻燃滚塑聚烯烃
US16/967,612 US12012542B2 (en) 2018-02-27 2019-02-20 Flame retardant rotomolded polyolefin
EP19760143.8A EP3759165A4 (fr) 2018-02-27 2019-02-20 Polyoléfine rotomoulée ignifuge
MX2020008934A MX2020008934A (es) 2018-02-27 2019-02-20 Poliolefina rotomoldeada ignifuga.
BR112020017274-0A BR112020017274A2 (pt) 2018-02-27 2019-02-20 Artigo de plástico retardador de chama, mistura de aditivo retardador de chama, e, processo para a produção de um artigo plástico oco.
CA3089890A CA3089890A1 (fr) 2018-02-27 2019-02-20 Polyolefine rotomoulee ignifuge
JP2020544904A JP2021515074A (ja) 2018-02-27 2019-02-20 難燃性回転成形ポリオレフィン

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US62/635,764 2018-02-27

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Citations (5)

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Publication number Priority date Publication date Assignee Title
GB2373507A (en) * 2000-12-12 2002-09-25 Ciba Sc Holding Ag Flame retardant polyolefin composition
US20060079612A1 (en) * 2002-04-10 2006-04-13 Malisa Troutman Flame retardant coatings
US20110092623A1 (en) * 2008-05-27 2011-04-21 Katsuhiro Yamanaka Flame retardant resin composition and molded article thereof
US8357324B2 (en) * 2009-04-21 2013-01-22 Basf Se Rotomolding process for polyethylene articles
WO2017013028A1 (fr) * 2015-07-20 2017-01-26 Basf Se Articles de polyoléfine ininflammables

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NL1014465C2 (nl) * 1999-03-01 2002-01-29 Ciba Sc Holding Ag Stabilisatorcombinatie voor het rotomoldingproces.
WO2010026230A1 (fr) * 2008-09-05 2010-03-11 Thor Gmbh Composition retardatrice de flamme renfermant un dérivé de l'acide phosphonique
KR20140017541A (ko) 2011-01-31 2014-02-11 바스프 에스이 고온에서 가공된 폴리에틸렌을 난연 처리하는 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2373507A (en) * 2000-12-12 2002-09-25 Ciba Sc Holding Ag Flame retardant polyolefin composition
US20060079612A1 (en) * 2002-04-10 2006-04-13 Malisa Troutman Flame retardant coatings
US20110092623A1 (en) * 2008-05-27 2011-04-21 Katsuhiro Yamanaka Flame retardant resin composition and molded article thereof
US8357324B2 (en) * 2009-04-21 2013-01-22 Basf Se Rotomolding process for polyethylene articles
WO2017013028A1 (fr) * 2015-07-20 2017-01-26 Basf Se Articles de polyoléfine ininflammables

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MX2020008934A (es) 2020-10-14
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CN112166148A (zh) 2021-01-01
JP2021515074A (ja) 2021-06-17
AR114401A1 (es) 2020-09-02
US20210087471A1 (en) 2021-03-25
BR112020017274A2 (pt) 2020-12-22
US12012542B2 (en) 2024-06-18
EP3759165A1 (fr) 2021-01-06
EP3759165A4 (fr) 2021-12-08

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